CHAPTER 5 GASES AND THE KINETIC

MOLECULAR THEORY
5.1 a) The volume of the liquid remains constant, but the volume of the gas increases to the volume of the larger
container.
b) The volume of the container holding the gas sample increases when heated, but the volume of the container
holding the liquid sample remains essentially constant when heated.
c) The volume of the liquid remains essentially constant, but the volume of the gas is reduced.
5.2 The particles in a gas are further apart than those are in a liquid.
a) The greater empty space between gas molecules allows gases to be more compressible than liquids.
b) The greater empty space between gas molecules allows gases to flow with less resistance (hindrance) than
liquids.
c) The large empty space between gas molecules limits their interaction, allowing all mixtures of gases to be
solutions.
d) The large empty space between gas molecules increases the volume of the gas, therefore decreasing the density.
5.3 The mercury column in the mercury barometer stays up due to the force exerted by the atmosphere on the mercury
in the outer reservoir just balancing the gravitational force on the mercury in the tube. Its height adjusts according
to the air pressure on the reservoir.
5.4 The pressure of mercury is its weight (force) per unit area. The weight, and thus the pressure, of the mercury
column is directly proportional to its height.
5.5 On a mountaintop, the air pressure is less, so the height of mercury it balances in the barometer is shorter than
at sea level where there is more air pressure.
5.6 The ratio of the heights of columns of mercury and water are inversely proportional to the ratio of the densities of
the two liquids.
2
2
H O Hg
Hg H O
h d
h d

2
2
Hg
H O Hg
H O
d
h xh
d

= ( )
3
2
13.5 g/mL 10 m 1 cm
725 mmHg
1.00 g/mL 1 mm 10 m

_ _ _


, , ,
= 978.75 = 979 cmH2O
5.7 P (mmH2O) =
2
2
Hg
H O Hg
H O
d
h xh
d

= ( )
3
2
13.5 g/mL 10 m 1 cm
755 mmHg
1.00 g/mL 1 mm 10 m

_ _ _


, , ,
= 1019.25 = 1.02 x 10
3
cmH2O
5.8 Plan: Use the conversion factors between pressure units:
1 atm = 760 mmHg = 760 torr = 101.325 kPa = 1.01325 bar
Solution:
a) ( )
760 mmHg
0.745 atm
1 atm
_

,
= 566.2 = 566 mmHg
b) ( )
1.01325 bar
992 torr
760 torr
_

,
= 1.32256 = 1.32 bar
c) ( )
1 atm
365 kPa
101.325 kPa
_

,
= 3.60227 = 3.60 atm
1
d) ( )
101.325 kPa
804 mmHg
760 mmHg
_

,
= 107.191 = 107 kPa
5.9 a) ( )
2
3
10 m 1 mm 1 atm
74.8 cmHg
1 cm 760 mmHg 10 m

_ _ _


, , ,
= 0.98421 = 0.984 atm
b) ( )
101.325 kPa
27.0 atm
1 atm
_

,
= 2735.775 = 2.74 x 10
3
kPa
c) ( )
1.01325 bar
8.50 atm
1 atm
_

,
= 8.6126 = 8.61 bar
d) ( )
760 torr
0.907 kPa
101.325 kPa
_

,
= 6.80306 = 6.80 torr
5.10 a) P(atm) = ( )
2
1 atm
2.75 x 10 mmHg
760 mmHg
_

,
= 0.361842 = 0.362 atm
b) P(atm) = ( )
1 atm
91 psi
14.7 psi
_

,
= 6.190 = 6.2 atm
c) P(atm) = ( )
6
5
1 atm
9.15 x 10 Pa
1.01325 x 10 Pa
_


,
= 90.303 = 90.3 atm
d) P(atm) = ( )
4
1 atm
2.44 x 10 torr
760 torr
_

,
= 32.105 = 32.1 atm
5.11 a) 1 atm = 1.01325 x 10
5
N/m
2
The force on 1 m
2
of ocean is 1.01325 x 10
5
N.
F = m x g
1.01325 x 10
5
N = mg
5
2
kg m
1.01325 x 10
s
= (mass) (9.81 m/s
2
)
mass = 1.03287 x 10
4
= 1.03 x 10
4
kg
b)
2
3 2
4
2
kg 10 g 10 m
1.03287 x 10
1 kg 1 cm m

_ _
_



,
, ,
= 1.03287 x 10
3
g/cm
2
(unrounded)
Height =
3
3
2
g 1 mL 1 cm
1.03287 x 10
22.6 g 1 mL cm
_ _
_


,
, ,
= 45.702 = 45.7 cm Os
5.12 The statement is incomplete with respect to temperature and mass of sample. The correct statement is: At constant
temperature and moles of gas, the volume of gas is inversely proportional to the pressure.
5.13 variable fixed
a) Volume; Temperature Pressure; Moles
b) Moles; Volume Temperature; Pressure
5.14 At constant temperature and volume, the pressure of the gas is directly proportional to the number of moles of the
gas. Verify this by examining the ideal gas equation. At constant T and V, the ideal gas equation becomes P =
n(RT/V) or P = n x constant.
5.15 a) n fixed b) P halved c) P fixed d) T doubled
2
5.16 a) As the pressure on a gas increases, the molecules move closer together, decreasing the volume. When the
pressure is tripled, the volume decreases to one third of the original volume at constant temperature (Boyles
Law).
b) As the temperature of a gas increases, the gas molecules gain kinetic energy. With higher energy, the gas
molecules collide with the walls of the container with greater force, which increases the size (volume) of the
container. If the temperature is increased by a factor of 2.5 (at constant pressure) then the volume will increase by
a factor of 2.5 (Charless Law).
c) As the number of molecules of gas increase, the force they exert on the container increases. This results in an
increase in the volume of the container. Adding two moles of gas to one mole increases the number of moles by a
factor of three, thus the volume increases by a factor of three (Avogadros Law).
5.17 V2 = V1 x (P1/P2) x (T2/T1)
a) If P2 is 1/4 of P1, then the volume would be increased by a factor of 4.
b) V2 = V1 x (101 kPa/202 kPa) x (155 K/310 K) = 1/4, so the volume would be decreased by a factor of 4.
c) V2 = V1 x (202 kPa/101 kPa) x (305 K/305 K) = 2, so the volume would be increased by a factor of 2.
5.18 Plan: This is Charless Law. Charless Law states that at constant pressure and with a fixed amount of gas, the
volume of a gas is directly proportional to the absolute temperature of the gas. The temperature must be lowered
to reduce the volume of a gas.
Solution:
2
2
1
1
T
V

T
V

at constant n and P
1
2
1 2
V
V
T T
V1 = 5.10 L; T1 = 198
o
C + 273 = 471K; V2 = 2.50 L T2 = ?
T2 =
,
_

L 5.10
L 2.50
K 471 = 230.88 K 273 = 42.12 = 42C
5.19
1
2
1 2
T
T
V V
= ( )
( )
( )
273 22 K
93 L
273 145 K
_


+
,
= 55.844 = 56 L
5.20 Plan: Since the volume, temperature, and pressure of the gas are changing, use the combined gas law.
Solution:
2
2 2
1
1 1
T
V P

T
V P

P1 = 153.3 kPa; V1 = 25.5 L; T1 = 298 K; P2 = 101.325 kPa; T2 = 273 K; V2 = ?

V2 =

,
_

,
_

2
1
1
2
1
P
P

T
T
V = ( )
273 K 153.3 kPa
25.5 L
298 K 101.325 kPa
_ _

, ,
= 35.3437 = 35.3 L
5.21
2
2 2
1
1 1
T
V P

T
V P

P1 = 745 torr; V1 = 3.65 L; T1 = 298 K; P2 = 367 torr; T2 = 14

o
C + 273 = 259 K; V2 = ?
V2 =

,
_

,
_

2
1
1
2
1
P
P

T
T
V
=
( )
,
_

,
_

torr 367
torr 745

K 298
K 259
L 65 . 3
= 6.4397 = 6.44 L
5.22 Plan: Given the volume, pressure, and temperature of a gas, the number of moles of the gas can be calculated using
the ideal gas equation, PV = nRT. The gas constant, R = 0.0821 Latm/molK, gives pressure in atmospheres
and temperature in Kelvin. The given pressure in torr must be converted to atmospheres and the temperature
converted to Kelvin.
3
Solution:
PV = nRT or n = PV/RT P = ( )
,
_

torr 760
atm 1
torr 228 = 0.300 atm; V = 5.0 L; T = 27
o
C + 273 = 300 K
PV (0.300 atm)(5.0 L)
n
L atm
RT
(0.0821 )(300 K)
mol K

g
g
= 0.060901 = 0.061 mol chlorine
5.23 PV = nRT
P = nRT / V =
( )
( ) ( )
3
3
L atm
1.47 x 10 mol 0.0821 273 26 K
1 mL 760 torr mol K
75.0 mL 1 atm 10 L

_
+

_ _
,


, ,
= 365.6655 = 366 torr
5.24 Plan: Solve the ideal gas equation for moles and convert to mass using the molar mass of ClF3.
Volume must be converted to L, pressure to atm and temperature to K.
Solution:
PV = nRT or n = PV/RT P =
( )

,
_

mmHg 760
atm 1
mmHg 699
= 0.91974 atm; V = 0.207 L
T = 45
o
C + 273 = 318 K
PV (0.91974 atm)(0.207 L)
n
L atm
RT
(0.0821 )(318 K)
mol K

g
g
= 0.0072923 mol ClF3
mass ClF3 =
( )
ClF mol 1
ClF g 92.45
ClF mol 0072923 . 0
3
3
3

,
_

= 0.67417 = 0.674 g ClF3

5.25 PV = nRT n = ( )

,
_

O N g 44.02
O N mol 1
O N g 0 . 75
2
2
2
= 1.70377 mol N2O
P =
L atm
(1.70377 mol )(0.0821 )(388 K)
nRT
mol K

V (3.1 L)

g
g = 17.5075 =18atm N2O

5.26 PV = nRT The total pressure of the gas is (85 + 14.7)psi.
n = PV / RT =
( ) ( ) ( )
( ) ( )
85 14.7 psi 1.5 L
1 atm
L atm 14.7 psi
0.0821 273 23 K
mol K
+
_

_
,
+

,
= 0.41863 = 0.42 mol SO2
5.27 Air is mostly N2 (28.02 g/mol), O2 (32.00 g/mol), and argon (39.95 g/mol). These heavy gases dominate the
density of dry air. Moist air contains H2O (18.02 g/mol). The relatively light water molecules lower the density of
the moist air.
5.28 The molar mass of H2 is less than the average molar mass of air (mostly N2, O2, and Ar), so air is denser. To
collect a beaker of H2(g), invert the beaker so that the air will be replaced by the lighter H2. The molar mass of
CO2 is greater than the average molar mass of air, so CO2(g) is more dense. Collect the CO2 holding the beaker
upright, so the lighter air will be displaced out the top of the beaker.
5.29 Gases mix to form a solution and each gas in the solution behaves as if it were the only gas present.
4
5.30 PA = XA PT The partial pressure of a gas (PA) in a mixture is directly proportional to its mole fraction (XA).
5.31 Plan: Using the ideal gas equation and the molar mass of xenon, 131.3 g/mol, we can find the density of xenon
gas at STP. Standard temperature is 0C and standard pressure is 1 atm. Do not forget that the pressure at STP is
exact and will not affect the significant figures.
Solution:
d = M P / RT =
( ) ( )
( )
131.3 g/ mol 1 atm
L atm
0.0821 273 K
mol K
_

,
= 5.8581 = 5.86 g/L
5.32 d = M P / RT =
( ) ( )
( ) ( )
137.86 g/mol 1.5 atm
L atm
0.0821 273 120 K
mol K
_
+

,
= 6.40905 = 6.4 g/L
5.33 Plan: Apply the ideal gas equation to determine the number of moles. Convert moles to mass and divide by the
volume to obtain density in g/L. Do not forget that the pressure at STP is exact and will not affect the significant
figures.
Solution:
n =
RT
PV
=
( ) ( )
( )
1 atm 0.0400L
L atm
0.0821 273 K
mol K
_

,
= 1.78465 x 10
3
= 1.78 x 10
3
mol AsH3
d =
volume
mass
=
( )
( )
( )
3
1.78465 x 10 mol 77.94 g/ mol
0.0400L

= 3.47740 = 3.48 g/L

5.34 d = M P / RT
M = dRT / P =
( ) ( ) ( )
( )
L atm
2.71 g/L 0.0821 273 0 K
mol K
3.00 atm
_
+

, = 20.24668 = 20.2 g/mol
Therefore, the gas is Ne.
5.35 Plan: Rearrange the formula PV = (m / M)RT to solve for molar mass: M = mRT / PV. Convert the mass
in ng to grams and volume in L to L. Temperature must be in Kelvin and pressure in torr.
Solution:
P =
( )
,
_

torr 760
atm 1
torr 388
=0.510526 atm T = 45
o
C + 273 = 318 K
V =
( )

,
_

L 1
L 10
206 . 0
-6

L
= 2.06 x 10
7
L mass =
( )

,
_

ng 1
g 10
ng 206
-9
= 2.06 x 10
7
g
M =
-7
-7
L atm
(2.06 x 10 g)(0.0821 )(318 K)
mRT
mol K

PV (0.510526 atm)(2.06 x 10 L)
_




,
g
g
= 51.1390 = 51.1 g/mol
5.36 M = mRT / PV =
( ) ( ) ( )
( ) ( )
3
L atm
0.103 g 0.0821 273 22 K
1 mL 760 mmHg mol K
747 mmHg 63.8 mL 1 atm 10 L

_
+

_ _
,


, ,
= 39.7809 = 39.8 g/mol
The molar masses are N2 = 28 g/mol, Ne = 20 g/mol, and Ar = 40 g/mol
Therefore, the gas is Ar.
5
5.37 Plan: Use the ideal gas equation to determine the number of moles of Ar and O2. The gases are combined
(nTOT = nAr + nO) into a 400 mL flask (V) at 27C (T). Determine the total pressure from nTOT, V, and T. Pressure
must be in units of atm, volume in units of L and temperature in K.
Solution:
PV = nRT
RT
PV
n
Moles Ar =
RT
PV
=
( ) ( )
( ) ( )
1.20 atm 0.600 L
L atm
0.0821 273 227 K
mol K
_
+

,
= 0.017539585 mol Ar (unrounded)
Moles O2 =
RT
PV
=
( ) ( )
( ) ( )
501 torr 0.200 L
1 atm
L atm 760 torr
0.0821 273 127 K
mol K
_

_
,
+

,
= 0.004014680 mol O2 (unrounded)
NTOT = n Ar + nO = 0.017539585 mol + 0.004014680 mol = 0.021554265 mol
P mixture =
nRT
V
=
( ) ( ) ( )
3
L atm
0.021554265 mol 0.0821 273 27 K
1 mL mol K
400 mL 10 L

_
+

_ ,

,
= 1.32720 = 1.33 atm
5.38 Total moles = nT = PV/RT =
( ) ( )
( ) ( )
3
626 mmHg 355 mL
1 atm 10 L
L atm 760 mmHg 1 mL
0.0821 273 35 K
mol K

_ _


_
, ,
+

,
= 0.011563657 mol (unrounded)
Moles Ne = nNe = (0.146 g Ne) (1 mol Ne / 20.18 g Ne) = 0.007234886 mol Ne (unrounded)
Moles Ar = nT nNe = (0.011563657 0.007234886) mol = 0.004328771 = 0.0043 mol Ar
5.39 d = M P / RT
At 17C
d = M P / RT =
( ) ( )
( ) ( )
28.8 g/ mol 744 torr
1 atm
L atm 760 torr
0.0821 273 17 K
mol K
_

_
,
+

,
= 1.18416 = 1.18 g/L
At 60.0C
d = M P / RT =
( ) ( )
( ) ( )
28.8 g/ mol 744 torr
1 atm
L atm 760 torr
0.0821 273 60.0 K
mol K
_

_
,
+

,
= 1.03125 = 1.03 g/L
5.40 PV = nRT
n / V = P / RT =
( )
( ) ( )
650. torr
1 atm
L atm 760 torr
0.0821 273 25 K
mol K
_

_
,

,
= 0.042005 = 0.0420 mol/L
5.41 Plan: The problem gives the mass, volume, temperature and pressure of a gas, so we can solve for molar mass
using M = mRT/PV. The problem also states that the gas is a hydrocarbon, which by, definition, contains only
carbon and hydrogen atoms. We are also told that each molecule of the gas contains five carbon atoms so we can
use this information and the calculated molar mass to find out how many hydrogen atoms are present and the
formula of the compound. Convert pressure to atm and temperature to K.
6
Solution:
M =
mRT
PV
=
( ) ( ) ( )
( ) ( )
L atm
0.482 g 0.0821 273 101 K
760 torr mol K
767 torr 0.204 L 1 atm
_
+

_
,

,
= 71.8869 g/mol (unrounded)
The carbon accounts for [5 (12 g/mol)] = 60 g/mol, thus, the hydrogen must make up the difference (72 60) =
12 g/mol. A value of 12 g/mol corresponds to 12 H atoms. (Since fractional atoms are not possible, rounding is
acceptable.)
Therefore, the molecular formula is C5H12.
5.42 PV = nRT
n = PV / RT
Molecules of air = n x Avogadros number = (PV / RT) x Avogadros number
Molecules of air =
( ) ( )
( ) ( )
23
1.00 atm 1.00 L
6.022 x 10 molecules
L atm mol
0.0821 273 25 K
mol K
_


_
,
+

,
= 2.461395 x 10
22
molecules (unrounded)
Molecules N2 = (2.461395 x 10
22
molecules) (78.08%/100%) = 1.921857 x 10
22
= 1.92 x 10
22
molecules N2
Molecules O2 = (2.461395 x 10
22
molecules) (20.94%/100%) = 5.154161 x 10
21
= 5.15 x 10
21
molecules O2
Molecules CO2 = (2.461395 x 10
22
molecules) (0.05%/100%) = 1.2306975 x 10
19
= 1 x 10
19
molecules CO2
Molecules Ar = (2.461395 x 10
22
molecules) (0.93%/100%) = 2.289097 x 10
20
= 2.3 x 10
20
molecules Ar
5.43 Plan: Since you have the pressure, volume and temperature, use the ideal gas equation to solve for the total
moles of gas.
Solution:
a) PV = nRT
n = PV / RT =
( ) ( )
( ) ( )
850. torr 21 L
1 atm
L atm 760 torr
0.0821 273 45 K
mol K
_

_
,
+

,
= 0.89961 = 0.90 mol gas
b) The information given in ppm is a way of expressing the proportion, or fraction, of SO2 present in the mixture.
Since n is directly proportional to V, the volume fraction can be used in place of the mole fraction used in equation
5.12. There are 7.95 x 10
3
parts SO2 in a million parts of mixture, so volume fraction = (7.95 x 10
3
/ 1 x 10
6
) =
7.95 x 10
3
.
Therefore,
2
SO
P
= volume fraction x PTOT = (7.95 x 10
3
) (850. torr) = 6.7575 = 6.76 torr.
5.44 Plan: We can find the moles of oxygen from the standard molar volume of gases (1 L of gas occupies 22.4 L at
STP) and use the stoichiometric ratio from the balanced equation to determine the moles of phosphorus that will
react with the oxygen.
Solution:
P4(s) + 5 O2(g) P4O10(s)
Mass P4 = ( )
2 4 4
2
2 2 4
1 mol O 1 mol P 123.88 g P
35.5 LO
22.4 L O 5 mol O 1 mol P
_ _ _

, , ,
= 39.2655 = 39.3 g P4
5.45 2 KClO3(s) 2 KCl(s) + 3 O2(g)
Moles O2 = n = PV / RT
Moles of O2 x mole ratio x molar mass KClO3 = g KClO3
Mass KClO3 =
( ) ( )
( ) ( )
3
3 3
2 3
752 torr 638 mL 2 mol KClO 122.55 g KClO 1 atm 10 L
L atm 760 torr 1 mL 3 mol O 1 mol KClO
0.0821 273 128 K
mol K

1
1
_ _ _ _
1


1 _
, , , ,
+
1
, ]
= 1.56660 = 1.57 g KClO3
7
5.46 Plan: To find the mass of PH3, write the balanced equation and find the number of moles of PH3 produced by
each reactant. The smaller number of moles of product indicates the limiting reagent. Solve for moles of
H2 using the standard molar volume (or use ideal gas equation).
Solution:
P4(s) + 6 H2(g) 4 PH3(g)
Moles hydrogen = ( )
1 mol
83.0 L
22.4 L
_

,
= 3.705357 mol H2 (unrounded)
PH3 from P4 = ( )
3 4
4
4 4
4 mol PH 1 mol P
37.5 g P
123.88 g P 1 mol P
_ _

, ,
= 1.21085 mol PH3
PH3 from H2 = ( )
3
2
2
4 mol PH
3.705357 mol H
6 mol H
_

,
= 2.470238 mol PH3
P4 is the limiting reactant.
Mass PH3 = ( )
3 3 4
4
4 4 3
4 mol PH 33.99 g PH 1 mol P
37.5 g P
123.88 g P 1 mol P 1 mol PH
_ _ _

, , ,
= 41.15676 = 41.2 g PH3
5.47 4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(l)
The moles are directly proportional to the volumes of the gases at the same temperature and pressure. Thus, the
limiting reactant may be found by comparing the volumes of the gases.
Mol NO from NH3 = ( )
3
3
4 L NO
35.6 L NH
4 L NH
_

,
= 35.6 L NO
Mol NO from O2 = ( )
2
2
4 L NO
40.5 L O
5 L O
_

,
= 32.4 L NO
O2 is the limiting reactant.
Mass NO = ( )
2
2
2 2
1 mol O 4 mol NO 30.01 g NO
40.5 LO
22.4 L O 5 mol O 1 mol NO
_ _ _

, , ,
= 43.4073 = 43.4 g NO
5.48 Plan: First, write the balanced equation. The moles of hydrogen produced can be calculated from the ideal gas
equation and then the stoichiometric ratio from the balanced equation is used to determine the moles of aluminum
that reacted. The problem specifies hydrogen gas collected over water, so the partial pressure of water must first
be subtracted. Table 5.2 reports pressure at 26C (25.2 torr) and 28C (28.3 torr), so take the average of the two
values to obtain the partial pressure of water at 27
o
C.
Solution:
2 Al(s) + 6 HCl(aq) 2 AlCl3(aq) + 3 H2(g)
Hydrogen pressure = total pressure pressure of water vapor =
(751 mmHg) [(28.3 + 25.2) torr / 2] = 724.25 torr (unrounded)
Moles of hydrogen:
PV =nRT
PV
n =
RT
=
( ) ( )
( )
3
724.25 torr 35.8 mL
1 atm 10 L
L atm 760 torr 1 mL
0.0821 273 27 K
mol K

1
1
_
_
1


1 _
,
,
+
1
, ]
g
g
= 0.00138514 mol H2
Mass of Al = ( )
2
2
2 mol Al 26.98 g Al
0.00138514 mol H
3 mol H 1 mol Al
_ _

, ,
= 0.024914 = 0.0249 g Al
8
5.49 First, write the balanced equation. The problem specifies hydrogen gas collected over water, so the partial
pressure of water must first be subtracted. Table 5.2 reports the vapor pressure of water at 18C (15.5 torr).
2 Li(s) + 2 H2O(l) 2 LiOH(aq) + H2(g)
Pressure H2 = total pressure vapor pressure of H2O = 725 mmHg 15.5 torr (1mmHg/1torr) = 709.5 mmHg
Moles H2 = ( )
2
1 mol H 1 mol Li
0.84 g Li
6.941 g Li 2 mol Li
_ _

, ,
= 0.0605100 mol H2
Volume H2 =
( ) ( )
L atm
0.0605100 mol 0.0821 273+ 18
nRT mol K
=
P
1 atm
709.5 mmHg
760 mmHg
1
_
1

1 ,
1
_ _
1


1
, , ]
g
g
= 1.5485 = 1.5 L H2
5.50 Plan: To find mL of SO2, write the balanced equation, convert the given mass of P4S3 to moles, use the molar ratio
to find moles of SO2, and use the ideal gas equation to find volume.
Solution:
P4S3(s) + 8 O2(g) P4O10(s) + 3 SO2(g)
Moles SO2 = ( )
4 3 2
4 3
4 3 4 3
1 mol P S 3 mol SO
0.800 g P S
220.09 g P S 1 mol P S
_ _

, ,
= 0.010905 mol SO2
Volume SO2 =
nRT
P
=
( ) ( ) ( )
2
3
L atm
0.010905 mol SO 0.0821 273 32 K
760 torr 1 mL mol K
725 torr 1 atm 10 L

_
+

_ _
,


, ,
= 286.249 = 286 mL SO2
5.51 Plan: First, write the balanced equation. Given the amount of xenon hexafluoride that reacts, we can find the
number of moles of silicon tetrafluoride gas formed. Then, using the ideal gas equation with the moles of gas, the
temperature and the volume, we can calculate the pressure of the silicon tetrafluoride gas.
Solution:
2 XeF6(s) + SiO2(s) 2 XeOF4(l) + SiF4(g)
Mole SiF4 = n = ( )
6 4
6
6 6
1 mol XeF 1 mol SiF
2.00 g XeF
245.3 g XeF 2 mol XeF
_ _

, ,
= 0.0040766 mol SiF4
Pressure SiF4 = P =
nRT
V
=
( ) ( ) ( )
4
L atm
0.0040766 mol SiF 0.0821 273 25 K
mol K
1.00 L
_
+

,

= 0.099737 = 0.0997 atm SiF4
5.52 2 PbS(s) + 3 O2(g) 2 PbO(g) + 2 SO2(g)
Moles SO2 from PbS = ( )
3
2
2 mol SO 10 g 1 mol PbS
3.75 kg PbS
1 kg 239.3 g PbS 2 mol PbS
_ _ _


, , ,
= 15.6707 mol SO2 (unrounded)
Moles of O2 =
PV
RT
=
( ) ( )
( ) ( )
2.0 atm 228 L
L atm
0.0821 273 220 K
mol K
_
+

,
= 11.266 mol O2
Moles SO2 from O2 = ( )
2
2
2
2 mol SO
11.266 mol O
3 mol O
_

,
= 7.5107mol SO2
O2 is the limiting reagent.
9
Volume SO2 = ( )
2
2
2 2
2 mol SO 22.4 L
11.266 mol O
3 mol O 1 mol SO
_ _

, ,
= 168.23 = 1.7 x 10
2
L SO2
5.53 As the temperature of the gas sample increases, the most probable speed increases. This will increase both the
number of collisions per unit time and the force of each collision with the sample walls. Thus, the gas pressure
increases.
5.54 At STP (or any identical temperature and pressure), the volume occupied by a mole of any gas will be identical.
This is because at the same temperature, all gases have the same average kinetic energy, resulting in the same
pressure.
5.55 The rate of effusion is much higher for a gas than its rate of diffusion. Effusion occurs into an evacuated space,
whereas diffusion occurs into another gas. It is reasonable to expect that a gas will escape faster into a vacuum than
it will into a space already occupied by another gas. The ratio of the rates of effusion and diffusion for two gases will
be the same since both are inversely proportional to the square root of their molar masses.
5.56 a) Mass O2 > mass H2
b)
2 2
H O
d d >
c) Identical
d) Average speed H2 > average speed O2
e) Effusion time H2 < effusion time O2
5.57 Plan: The molar masses of the three gases are 2.016 for H2 (Flask A), 4.003 for He (Flask B), and 16.04 for CH4
(Flask C). Since hydrogen has the smallest molar mass of the three gases, 4 g of H2 will contain more gas
molecules (about 2 moles worth) than 4 g of He or 4 g of CH4. Since helium has a smaller molar mass than
methane, 4 g of He will contain more gas molecules (about 1 moles worth) than 4 g of CH4 (about 0.25 moles
worth).
Solution:
a) PA > PB > PC The pressure of a gas is proportional to the number of gas molecules. So, the gas sample with
more gas molecules will have a greater pressure.
b) EA = EB = EC Average kinetic energy depends only on temperature. The temperature of each gas sample is
273 K, so they all have the same average kinetic energy.
c) rateA > rateB > rateC When comparing the speed of two gas molecules, the one with the lower mass travels
faster.
d) total EA > total EB > total EC Since the average kinetic energy for each gas is the same (part b of this problem)
then the total kinetic energy would equal the average times the number of molecules. Since the hydrogen flask
contains the most molecules, its total kinetic energy will be the greatest.
e) dA = dB = dC Under the conditions stated in this problem, each sample has the same volume, 5 L, and the same
mass, 4 g. Thus, the density of each is 4 g/5 L = 0.8 g/L.
5.58 Plan: To find the ratio of effusion rates, calculate the inverse of the ratio of the square roots of the molar masses
(equation 5.14, Grahams Law).
Solution:
2
6
Rate H
Rate UF
=
6
2
Molar Mass UF
Molar Mass H
=
352.0 g/mol
2.016 g/ mol
= 13.2137 = 13.21
5.59 To find the ratio of effusion rates, calculate the inverse of the ratio of the square roots of the molar masses
(equation 5.14).
2
Rate O
Rate Kr
=
2
Molar Mass Kr
Molar Mass O
=
83.80 g/mol
32.00 g/ mol
= 1.618255 = 1.618
10
5.60 a) The gases have the same average kinetic energy because they are at the same temperature. The heavier
Ar atoms are moving slower than the lighter He atoms to maintain the same average kinetic energy. Therefore,
Curve 1 better represents the behavior of Ar.
b) A gas that has a slower molecular speed would effuse more slowly, so Curve 1 is the better choice.
c) Fluorine gas exists as a diatomic molecule, F2, with M = 38.00 g/mol. Therefore, F2 is much closer in size to
Ar (39.95 g/mol) than He (4.003 g/mol), so Curve 1 more closely represents F2s behavior.
5.61 a) Curve 1
b) Curve 2
c) Curve 2
5.62 Plan: To find the ratio of effusion rates, calculate the inverse of the ratio of the square roots of the molar masses
(equation 5.14). Then use the ratio of effusion rates to find the time for the F2 effusion.
Solution:
2
Rate He
Rate F
=
2
Molar Mass F
Molar Mass He
=
38.00 g/ mol
4.003 g/ mol
= 3.08105 (unrounded)
2
Rate He
Rate F
=
2
Time F
Time He

2
Time F 3.08105
=
1.00 4.55 min He
Time F2 = 14.01878 = 14.0 min
5.63
2
Rate H
Rate Unknown
=
2
Time Unk
Time H
=
2
Molar Mass Unk
Molar Mass H
11.1 min
2.42 min
=
Molar Mass Unk
2.016 g/ mol
4.586777 =
Molar Mass Unk
2.016 g/ mol
Molar Mass unknown = 42.41366 = 42.4 g/mol
5.64 Plan: White phosphorus is a molecular form of the element phosphorus consisting of some number, x, of
phosphorus atoms. Use the relative rates of effusion of white phosphorus and neon to determine the molar mass of
white phosphorous. From the molar mass of white phosphorus, determine the number of phosphorus atoms, x, in
one molecule of white phosphorus.
Solution:
x
Rate P
Rate Ne
= 0.404 =
x
Molar Mass Ne
Molar Mass P

(0.404)
2
=
x
Molar Mass Ne
Molar Mass P
=
x
20.18 g/mol
Molar Mass P
0.163216 =
x
20.18 g/mol
Molar Mass P
Molar Mass Px = 123.6398 g/mol
x
123.6398 g 1 mol P
mol P 30.97 g P
_ _

, ,
= 3.992244 = 4 mol P/mol Px or 4 atoms P/molecule Px
Thus, 4 atoms per molecule, so Px = P4.
5.65 a) 0C = 273 K 30C = 303 K (4.003 g He/mol) (1 kg / 10
3
g) = 0.004003 kg/mol
urms He (at 0C) =
( )
2 2
J
3 8.314 273 K
kg m /s mol K
0.004003 kg/mol J
_

_
,


,
= 1.3042 x 10
3
= 1.30 x 10
3
m /s
11
urms He (at 30C) =
( )
2 2
J
3 8.314 303 K
kg m /s mol K
0.004003 kg/mol J
_

_
,


,
= 1.3740 x 10
3
= 1.37 x 10
3
m/s
b) (131.3 g Xe/mol) (1 kg / 10
3
g) = 0.1313 kg/mol
urms He (at 0C) =
( )
2 2
J
3 8.314 303 K
kg m /s mol K
0.1313 kg/mol J
_

_
,


,
= 239.913 m/s (unrounded)
Rate He / Rate Xe = (1.3740 x 10
3
m/s) / (239.913 m/s) = 5.727076 = 5.72
He molecules travel at almost 6x the speed of Xe molecules.
c) EHe = 1/2 mv
2
= (1/2) (0.004003 kg/mol) (1.3740 x 10
3
m/s)
2
(1J/(kgm
2
/s
2
) = 3778.58 = 3.78 x 10
3
J/mol
EXe = 1/2 mv
2
= (1/2) (0.1313 kg/mol) (239.913 m/s)
2
(1J/(kgm
2
/s
2
) = 3778.69 = 3.78 x 10
3
J/mol
d) (3778.58 J/mol) (1 mol He / 6.022 x 10
23
atoms He) = 6.2746 x 10
21
= 6.27 x 10
21
J/He atom
5.66 Intermolecular attractions cause the real pressure to be less than ideal pressure, so it causes a negative deviation.
The size of the intermolecular attraction is related to the constant a. According to Table 5.4,
2
N
a
= 1.39,
Kr
a
= 2.32
and
2
CO
a
= 3.59. Therefore, CO2 experiences a greater negative deviation in pressure than the other two gases: N2
< Kr < CO2.
5.67 Molecular size causes a positive deviation from ideal behavior. Thus, VReal Gases > VIdeal Gases. The
molecular volume is related to the constant b. According to Table 5.4,
2
H
b
= 0.0266,
2
O
b
= 0.0318and
2
Cl
b
= 0.0562. Therefore, the order is H2 < O2 < Cl2.
5.68 Nitrogen gas behaves more ideally at 1 atm than at 500 atm because at lower pressures the gas molecules are
farther apart. An ideal gas is defined as consisting of gas molecules that act independently of the other gas
molecules. When gas molecules are far apart, they act ideally, because intermolecular attractions are less
important and the volume of the molecules is a smaller fraction of the container volume.
5.69 At 150C. At higher temperatures, intermolecular attractions become less important and the volume occupied by the
molecules becomes less important.
5.70 Do not forget to multiply the area of each side by two.
Surface area of can = 2 (40.0 cm) (15.0 cm) + 2 (40.0 cm) (12.5 cm) + 2 (15.0 cm) (12.5 cm)
= 2.575 x 10
3
cm
2
(unrounded)
Total force = (2.575 x 10
3
cm
2
) (1 in/2.54 cm)
2
(14.7 lb/in
2
) = 5.8671 x 10
3
= 5.87 x 10
3
lbs
5.71 Plan: Use the Ideal Gas Equation to find the number of moles of O2. Moles of O2 combine with Hb in a
4:1 ratio. Divide the mass of Hb by the number of moles to obtain molar mass, g/mol.
Solution:
PV = nRT
Moles O2 =
PV
RT
=
( ) ( )
( ) ( )
3
743 torr 1.53 mL
1 atm 10 L
L atm 760 torr 1 mL
0.0821 273 37 K
mol K

_ _


_
, ,
+

,
= 5.87708 x 10
5
mol O2 (unrounded)
Moles Hb = ( )
-5
2
2
1 mol Hb
5.87708 x 10 mol O
4 mol O
_

,
= 1.46927 x 10
5
mol Hb (unrounded)
Molar mass hemoglobin = (1.00 g Hb) / (1.46927 x 10
5
mol Hb) = 6.806098 x 10
4
= 6.81 x 10
4
g/mol
12
5.72 Reaction 1: 2 NaHCO3(s) Na2CO3(s) + H2O(l) + CO2(g)
Moles CO2 = (1.00 g NaHCO3) (1 mol NaHCO3 / 84.01 g NaHCO3) (1 mol CO2 /2 mol NaHCO3)
= 5.95167 x 10
3
mol CO2 (unrounded)
V = nRT / P =
( )
( ) ( )
3
3
L atm
5.95167 x10 mol 0.0821 273 200. K
1 mL mol K
0.975 atm 10 L

_
+

_
,


,
= 237.049 = 237 mL CO2 Reaction 1
Reaction 2: NaHCO3(s) + H
+
(aq) H2O(l) + CO2(g) + Na
+
(aq)
Moles CO2 = (1.00 g NaHCO3) (1 mol NaHCO3 / 84.01 g NaHCO3) (1 mol CO2 /1 mol NaHCO3)
= 1.1903 x 10
2
mol CO2 (unrounded)
V = nRT / P =
( )
( ) ( )
2
3
L atm
1.1903 x 10 mol 0.0821 273 200. K
1 mL mol K
0.975 atm 10 L

_
+

_
,


,
= 474.0986 = 474 mL CO2 Reaction 2
5.73 Plan: Convert the mass of Cl2 to moles and use the ideal gas law and van der Waals equation to
find the pressure of the gas.
Solution:
a) Moles Cl2: ( )
3
2
2
2
1 mol Cl 10 g
0.5850 kg Cl
1 kg 70.90 g Cl
_ _

, ,
= 8.2510578 mol
Ideal gas equation: PV = nRT
PIGL = nRT/V =
( ) ( )
L atm
8.2510578 mol 0.0821 273 225 K
mol K
15.00 L
_
+

,
= 22.4901 = 22.5 atm
b) ( )
2
2
n a
P V nb nRT
V
_
+

,
PVDW =
2
2
nRT n a
V nb V

From Table 5.4: a =

2
2
atm L
6.49
mol
g
; b = 0.0562
L
mol
n = 8.2510578 mol from Part (a)
PVDW =
( ) ( ) ( )
( )
( )
( )
2
2
2
2 2
2
2
atm L
L atm
8.2510578 mol Cl 6.49
8.2510578 mol Cl 0.0821 273 225 K
mol
mol K
L
15.00 L
15.00 L 8.2510578 mol Cl 0.0562
mol
_
_
+

, ,

,
= 21.24378 = 21.2 atm
5.74 a) Molar Mass I = mRT / PV =
( ) ( ) ( )
( ) ( )
3
L atm
0.1000 g 0.08206 273.15 70.00 K
1 mL mol K
0.05951 atm 750.0 mL 10 L

_
+

_
,


,
= 63.0905 = 63.09 g I / mol
Molar Mass II = mRT / PV =
( ) ( ) ( )
( ) ( )
3
L atm
0.1000 g 0.08206 273.15 70.00 K
1 mL mol K
0.07045 atm 750.0 mL 10 L

_
+

_
,


,
= 53.293 = 53.29 g II / mol
13
Molar Mass III = mRT / PV =
( ) ( ) ( )
( ) ( )
3
L atm
0.1000 g 0.08206 273.15 70.00 K
1 mL mol K
0.05767 atm 750.0 mL 10 L

_
+

_
,


,
= 65.10349 = 65.10 g III / mol
b) % H in I = 100% 85.63% = 14.37% H
% H in II = 100% 81.10% = 18.90% H
% H in III = 100% 82.98% = 17.02% H
Assume 100 grams of each so the mass percentages are also the grams of the element.
I
(85.63 g B) (1 mol B / 10.81 g B) = 7.921369 mol B (unrounded)
(14.37 g H) (1 mol H / 1.008 g H) = 14.25595 mol H (unrounded)
Dividing by the smaller value (7.921369) gives B = 1 and H = 1.7997
The hydrogen value is not close enough to a whole number to round. Thus, both amounts need to be
multiplied by the smallest value to get near whole numbers. This value is 5. Multiplying by 5 gives B = 5
and H = 9. The empirical formula is B5H9, which has a formula mass of 63.12 g/mol. The empirical
formula mass is near the molecular mass from part a. Therefore, the empirical and molecular formulas
are both B5H9.
II
(81.10 g B) (1 mol B / 10.81 g B) = 7.50231 mol B (unrounded)
(18.90 g H) (1 mol H / 1.008 g H) = 18.750 mol H (unrounded)
Dividing by the smaller value (7.50231) gives B = 1 and H = 2.4992
The hydrogen value is not close enough to a whole number to round. Thus, both amounts need to be
multiplied by the smallest value to get near whole numbers. This value is 2. Multiplying by 2 gives B = 2
and H = 5. The empirical formula is B2H5, which has a formula mass of 26.66 g/mol. Dividing the
molecular formula mass by the empirical formula mass gives the relationship between the
formulas: (53.29) / (26.66) = 2. The molecular formula is two times the empirical formula, or B4H10.
III
(82.98 g B) (1 mol B / 10.81 g B) = 7.6762 mol B (unrounded)
(17.02 g H) (1 mol H / 1.008 g H) = 16.8849 mol H (unrounded)
Dividing by the smaller value (7.6762) gives B = 1 and H = 2.2
The hydrogen value is not close enough to a whole number to round. Thus, both amounts need to be
multiplied by the smallest value to get near whole numbers. This value is 5. Multiplying by 5 gives B = 5
and H = 11. The empirical formula is B5H11, which has a formula mass of 65.14 g/mol. The empirical
formula mass is near the molecular mass from part a. Therefore, the empirical and molecular formulas
are both B5H11.
c)
2
Rate SO
Rate IV
=
2
Molar Mass IV
Molar Mass SO
250.0 mL
13.04 min
350.0 mL
12.00 min
_

,
_

,
= 0.657318 =
Molar Mass Unk
64.07 g/ mol

Molar Mass IV = 27.6825 = 27.68 g/mol
14
IV
% H in IV = 100% 78.14% = 21.86% H
Assume 100 grams of each so the mass percentages are also the grams of the element.
(78.14 g B) (1 mol B / 10.81 g B) = 7.22849 mol B (unrounded)
(21.86 g H) (1 mol H / 1.008 g H) = 21.6865 mol H (unrounded)
Dividing by the smaller value (7.22849) gives B = 1 and H = 3.000
The empirical formula is BH3, which has a formula mass of 13.83 g/mol. Dividing the molecular
formula mass by the empirical formula mass gives the relationship between the formulas:
(27.68) / (13.83) = 2. The molecular formula is two times the empirical formula, or B2H6.
5.75 Plan: Partial pressures and mole fractions are calculated from Daltons Law of Partial Pressures: PA = XA(Ptotal)
Solution:
a) Convert each mole percent to a mole fraction by dividing by 100%.
PNitrogen = XNitrogen PTotal = (0.786) (1.00 atm) (760 torr / 1 atm) = 597.36 = 597 torr N2
POxygen = XOxygen PTotal = (0.209) (1.00 atm) (760 torr / 1 atm) = 158.84 = 159 torr O2
PCarbon Dioxide = XCarbon Dioxide PTotal = (0.0004) (1.00 atm) (760 torr / 1 atm) = 0.304 = 0.3 torr CO2
PWater = XWater PTotal = (0.0046) (1.00 atm) (760 torr / 1 atm) = 3.496 = 3.5 torr O2
b) Mole fractions can be calculated by rearranging Daltons Law of Partial Pressures:
XA = PA/Ptotal and multiply by 100 to express mole fraction as percent.
PTotal = (569 + 104 + 40 + 47) torr = 760 torr
N2: [(569 torr) / (760 torr)] x 100% = 74.8684 = 74.9 mol% N2
O2: [(104 torr) / (760 torr)] x 100% = 13.6842 = 13.7 mol% O2
CO2: [(40 torr) / (760 torr)] x 100% = 5.263 = 5.3 mol% CO2
H2O: [(47 torr) / (760 torr)] x 100% = 6.1842 = 6.2 mol% CO2
c) Number of molecules of O2 can be calculated using the Ideal Gas Equation and Avogadros number.
PV = nRT
Moles O2 =
PV
RT
=
( ) ( )
( ) ( )
104 torr 0.50 L
1 atm
L atm 760 torr
0.0821 273 37 K
mol K
_

_
,
+

,
= 0.0026883 mol O2
Molecules O2 = ( )
23
2
2
2
6.022 x 10 molecules O
0.0026883 mol O
1 mol O
_

,
= 1.6189 x 10
21
= 1.6 x 10
21
molecules O2
5.76 Atoms Rn = ( )
4
15 23
1.373 x 10 Rn atoms
1.0 x 10 Ra atoms 1 mol Ra 6.022 x 10 Ra atoms 3600 s 24 h
1.0 g Ra
226 g Ra 1 mol Ra s h day
_ _


_ _ _ _ ,


,
, , ,


,
= 3.16094 x 10
15
Rn atoms / day (unrounded)
V = nRT / P =
( )
( )
( )
15
23
1 mol Rn L atm
3.16094 x 10 Rn atoms 0.0821 273 K
mol K 6.022 x 10 Rn atoms
1.00 atm
1 _
_
1


,
1 , ]
= 1.17647 x 10
7
= 1.2 x 10
7
L Rn
5.77 Plan: For part a, since the volume, temperature, and pressure of the gas are changing, use the combined gas law.
For part b, use the ideal gas equation to solve for moles of air and then moles of N2.
Solution:
a)
2
2 2
1
1 1
T
V P

T
V P

P1 = ( )
1 atm
1400. mmHg
760 mmHg
_

,
= 1.8421 atm; V1 = 208 mL;
T1 = 286 K; P2 = 1 atm; T2 = 273 K; V2 = ?
15
V2 =

,
_

,
_

2
1
1
2
1
P
P

T
T
V
= ( )
298 K 1.8421 atm
208 mL
286 K 1atm
_
_

,
,
= 399.23 mL = 4 x 10
2
mL
b) Mole air = n =
PV
RT
=
( ) ( )
( )
1.8421 atm 0.208 L
L atm
0.0821 286 K
mol K
_

,
= 0.016318 mol air
Mole N2 = ( )
2
77% N
0.016318 mol
100%
_

,
= 0.0125649 = 0.013 mol N2
5.78 The balanced equation and reactant amounts are given, so the first step is to identify the limiting reactant.
Moles NO2 from Cu = ( )
3 2
3
2 mol NO 8.95 g Cu 1 mol Cu
4.95 cm
63.55 g Cu 1 mol Cu cm
_ _
_

,
, ,
= 1.394256 mol NO2 (unrounded)
Moles NO2 from HNO3 = ( )
3
3 3 2
3
3
68.0% HNO 1 mol HNO 2 mol NO 1 cm 1.42 g
230.0 mL
100% 1 mL 63.02 g 4 mol HNO cm
_ _ _ _ _


, , , , ,
= 1.7620 mol NO2 (unrounded)
Since less product can be made from the copper, it is the limiting reactant and excess nitric acid will be left after
the reaction goes to completion. Use the calculated number of moles of NO2 and the given temperature and
pressure in the ideal gas equation to find the volume of nitrogen dioxide produced. Note that nitrogen dioxide is
the only gas involved in the reaction.
V =
nRT
P
=
( ) ( ) ( )
( )
2
L atm
1.394256 mol NO 0.0821 273.2 28.2 K
760 torr mol K
735 torr 1 atm
_
+

_
,

,
= 35.67428 = 35.7 L NO2
5.79 a) n = PV / RT =
( ) ( )
( ) ( )
3
1.0 atm 1200 mL
10 L
L atm 1 mL
0.0821 273 37 K
mol K

_


_
,
+

,
= 0.047149 = 0.047 mol air
b) Molecules = (0.047149 mol air) (6.022 x 10
23
molecules air / mol air)
= 2.83931 x 10
22
= 2.8 x 10
22
molecules air
5.80 The reaction is: 2 NaN3(s) 2 Na(s) + 3 N2(g)
The vapor pressure of water (Table 5.2) at 26C is 25.2 torr (= 25.2 mmHg).
Volume = nRT/ P =
( ) ( )
( ) ( )
3 2
3
3 3
1 mol NaN 3 mol N L atm
50.0 g NaN 0.0821 273 26 K
65.02 g NaN 2 mol NaN mol K
760 mmHg
1 atm 745.5 25.2 mmHg
1 _ _
_
+
1
, _ 1 , , ]

,
= 29.8764 = 29.9 L N2
5.81 It is necessary to determine both the empirical formula and the molar mass of the gas.
Empirical formula:
Assume 100.0 grams of sample to make the percentages of each element equal to the grams of that
element. Thus, 64.81% C = 64.81 g C, 13.60% H = 13.60 g H, and 21.59% O = 21.59 g O.
Moles C = (64.81 g C) (1 mol C / 12.01 g C) = 5.39634 mol C (unrounded)
Moles H = (13.60 g H) (1 mol H / 1.008 g H) = 13.49206 mol H (unrounded)
Moles O = (21.59 g O) (1 mol O / 16.00 g O) = 1.349375 mol O (unrounded)
16
Divide by the smallest number of moles (O):
C = (5.39634 mol) / (1.349375 mol) = 4
H = (13.49206 mol) / (1.349375 mol) = 10
O = (1.349375 mol) / (1.349375 mol) = 1
Empirical formula = C4H10O (empirical formula mass = 74.12 g/mol)
Molar Mass:
M = mRT / PV =
( ) ( ) ( )
( ) ( )
L atm
2.57 g 0.0821 273 25 K
mol K
0.420 atm 2.00 L
_
+

, = 74.85 g/mol (unrounded)
Molecular formula:
Since the molar mass and the empirical formula mass are similar, the empirical and molecular formulas
must both be: C4H10O
5.82 Plan: The empirical formula for aluminum chloride is AlCl3 (Al
3+
and Cl

). The empirical formula mass is

(133.33 g/mol). Calculate the molar mass of the gaseous species from the ratio of effusion rates. This molar mass,
divided by the empirical weight, should give a whole number multiple that will yield the molecular formula.
Solution:
Rate Unk
Rate He
= 0.122 =
Molar Mass He
Molar Mass Unk
0.122 =
4.003 g/mol
Molar Mass Unk
Molar mass Unknown = 268.9465 g/mol
The whole number multiple is 268.9465/133.33, which is about 2. Therefore, the molecular formula of the
gaseous species is 2 x (AlCl3) = Al2Cl6.
5.83 a) 2 C8H18(l) + 25 O2(g) 16 CO2(g) + 18 H2O (g)
Moles products = ( )
8 18
8 18
8 18 8 18
1 mol C H 34 mol gas
100. gC H
114.22 g C H 2 mol C H
_ _

, ,
= 14.883558 mol gas (unrounded)
V = nRT / P =
( ) ( ) ( )
( )
L atm
14.883558 mol gas 0.0821 273 350 K
760 torr mol K
735 torr 1 atm
_
+

_
,

,
= 787.162 = 787 L gas
b) Moles O2 = ( )
8 18 2
8 18
8 18 8 18
1 mol C H 25 mol O
100. g C H
114.22 g C H 2 mol C H
_ _

, ,
= 10.94379 mol O2 (unrounded)
Moles other gases = (10.94379 mol O2) [(78 + 1.0)%] / (21%) = 41.1695 mol gas (unrounded)
V = nRT / P =
( ) ( ) ( )
( )
L atm
41.1695 mol gas 0.0821 273 350 K
760 torr mol K
735 torr 1 atm
_
+

_
,

,
= 2177.37 L residual air (unrounded)
Total volume of gaseous exhaust = 787.162 L + 2177.37 L = 2964.53 = 2.96 x 10
3
L
5.84 Plan: First, write the balanced equation for the reaction: 2 SO2 + O2 2 SO3. The total number of moles of
gas will change as the reaction occurs since 3 moles of reactant gas forms 2 moles of product gas. From
the volume, temperature, and pressures given, we can calculate the number of moles of gas before and after the
reaction using ideal gas equation. For each mole of SO3 formed, the total number of moles of gas decreases by 1/2
mole. Thus, twice the decrease in moles of gas equals the moles of SO3 formed.
17
Solution:
Moles of gas before and after reaction
Initial moles =
PV
RT
=
( ) ( )
( )
1.95 atm 2.00 L
L atm
0.0821 900. K
mol K
_

,
= 0.05278116 mol (unrounded)
Final moles =
PV
RT
=
( ) ( )
( )
1.65 atm 2.00 L
L atm
0.0821 900. K
mol K
_

,
= 0.04466098 mol (unrounded)
Moles of SO3 produced = 2 x decrease in the total number of moles
= 2 x (0.05278116 mol 0.04466098 mol)
= 0.01624036 = 1.62 x 10
2
mol
Check: If the starting amount is 0.0528 total moles of SO2 and O2, then x + y = 0.0528 mol,
where x = mol of SO2 and y = mol of O2. After the reaction:
(x z) + (y 0.5z) + z = 0.0447 mol
Where z = mol of SO3 formed = mol of SO2 reacted = 2(mol of O2 reacted).
Subtracting the two equations gives:
x (x z) + y (y 0.5z) z = 0.0528 0.0447
z = 0.0163 mol SO3
The approach of setting up two equations and solving them gives the same result as above.
5.85 The reaction is: 2 NCl3(l)

N2(g) + 3 Cl2(g)
The decomposition of all the NCl3 means that the final pressure must be due to the N2 and the Cl2. The product
gases are present at a 1:3 ratio, and the total moles are 4.
a) Partial pressure N2 = Pnitrogen = Xnitrogen Ptotal = (1 mol N2 / 4 mol total) (754 mmHg)
= 188.5 = 188 mmHg N2
Partial pressure Cl2 = Pnitrogen = Xnitrogen Ptotal = (3 mol Cl2 / 4 mol total) (754 mmHg) = 565.5 = 566 mmHg Cl2
b) The mass of NCl3 may be determined several ways. Using the partial pressure of Cl2 gives:
Moles Cl2 = n =
PV
RT
=
( ) ( )
( ) ( )
565.5 mmHg 2.50L
1 atm
L atm 760 mmHg
0.0821 273 95 K
mol K
_

_
,
+

,
= 0.0615698 mol Cl2
Mass NCl3 = ( )
3 3
2
2 3
2 mol NCl 120.36 g NCl
0.0615698 mol Cl
3 mol Cl 1 mol NCl
_ _

, ,
= 4.94036 = 4.94 g NCl3
5.86 The reaction is: 2 NH4NO3(s) 2 N2(g) + O2(g) + 4 H2O(g)
Moles gas = ( )
3
4 3
4 3
4 3 4 3
1 mol NH NO 10 g 7 mol Gas
15.0 kg NH NO
1 kg 80.05 g NH NO 2 mol NH NO
_ _ _


, , ,
= 655.840 mol gas (unrounded)
V = nRT / P =
( ) ( ) ( )
( )
L atm
655.840 mol Gas 0.0821 273 307 K
mol K
1.00 atm
_
+

, = 3.1229789 x 10
4
= 3.12 x 10
4
L
5.87 Assume 100 grams of sample, thus 33.01% Si is equivalent to 33.01 grams Si, and 66.99% F is equivalent to
66.99 grams of F.
Moles Si = (33.01 g Si) (1 mol Si / 28.09 g Si) = 1.17515 mol Si (unrounded)
Moles F = (66.99 g F) (1 mol F / 19.00 g F) = 3.525789 mol F (unrounded)
Dividing by the smaller value (1.17515) gives an empirical formula of SiF3 (empirical formula mass = 85 g/mol).
M = mRT / PV =
( ) ( ) ( )
( ) ( )
L atm
2.60 g 0.0821 273 27 K
mol K
1.50 atm 0.250 L
_
+

, = 170.768 g/mol (unrounded)
18
The molar mass is twice the empirical formula mass, so the molecular formula must be twice the empirical
formula, or 2 x SiF3 = Si2F6.
5.88 a) A preliminary equation for this reaction is __CxHyNz + n O2 4 CO2 + 2 N2 + 10 H2O.
Since the organic compound does not contain oxygen, the only source of oxygen as a reactant is oxygen gas. To
form 4 volumes of CO2 would require 4 volumes of O2 and to form 10 volumes of H2O would require 5 volumes
of O2. Thus, 9 volumes of O2 was required.
b) Since the volume of a gas is proportional to the number of moles of the gas we can equate volume and moles.
From a volume ratio of 4 CO2:2 N2:10 H2O we deduce a mole ratio of 4 C:4 N:20 H or 1 C:1 N:5 H for an
empirical formula of CH5N.
5.89 a) 2 x 10
6
blue particles and 2 x 10
6
black particles
b) 2 x 10
6
blue particles and 2 x 10
6
black particles
c) Final pressure in C = (2/3) (750 torr) = 500 torr
d) Final pressure in B = (2/3) (750 torr) = 500 torr
5.90 Plan: To find the factor by which a divers lungs would expand, find the factor by which P changes from 125 ft to
the surface, and apply Boyles Law. To find that factor, calculate Pseawater at 125 ft by converting the given depth
from ft-seawater to mmHg to atm and adding the surface pressure (1.00 atm).
Solution:
P (H2O) = ( )
2
-3
12 in 2.54 cm 10 m 1 mm
125 ft
1 ft 1 in 1 cm 10 m

_
_ _ _


, , ,
,
= 3.81 x 10
4
mmH2O
P (Hg):
H O Hg
2
Hg H O
2
=
h d
h d

4
2
Hg
3.81 x 10 mmH O 13.5 g/mL
=
1.04 g/mL h
hHg = 2935.1111 mmHg
P (Hg) = ( )
1 atm
2935.11111 mmHg
760 mm Hg
_

,
= 3.861988 atm (unrounded)
Ptotal = (1.00 atm) + (3.861988 atm) = 4.861988 atm (unrounded)
Use Boyles Law to find the volume change of the divers lungs:
P1V1 = P2V
2 1
1 2
V P
=
V P

2
1
V 4.861988 atm
=
V 1 atm
= 4.86
To find the depth to which the diver could ascend safely, use the given safe expansion factor (1.5) and the
pressure at 125 ft, P125, to find the safest ascended pressure, Psafe.
P125 / Psafe = 1.5
Psafe = P125 / 1.5 = (4.861988 atm) / 1.5 = 3.241325 atm (unrounded)
Convert the pressure in atm to pressure in ft of seawater using the conversion factors above. Subtract this distance
from the initial depth to find how far the diver could ascend.
h (Hg): ( )
760 mmHg
4.861988 - 3.241325 atm
1 atm
_

,
= 1231.7039 mmHg
H O Hg
2
Hg H O
2
=
h d
h d

H O
2
13.5 g/mL
=
1231.7039 mmHg 1.04 g/mL
h
H O
2
h
= 15988.464 mm
( )
3
2
10 m 1.094 yd 3 ft
15988.464 mmH O
1 mm 1 m 1 yd

_ _ _

,
, ,
= 52.4741 ft
Therefore, the diver can safely ascend 52.5 ft to a depth of (125 52.4741) = 72.5259 = 73 ft.
19
5.91 The balanced equation is: CaF2(s) + H2SO4(aq) 2 HF(g) + CaSO4(s)
T = PV / nR =
( ) ( )
2
2
2 2
875 torr 8.63 L
1 atm
760 torr
1 mol CaF 2 mol HF L atm
15.0 g CaF 0.0821
78.08 g CaF 1 mol CaF mol K
_

1 _ _
, _
1
, 1 , , ]
= 314.9783 K
The gas must be heated to 315 K.
5.92 The moles may be found using the ideal gas equation. Moles times Avogadros number gives the molecules.
Molecules =
( )
( )
( )
8
3 23 10 mmHg 1 mL
1 atm 10 L 6.022 x 10 molecules
L atm 760 mmHg 1 mL mol
0.0821 500 K
mol K

_ _ _


_
, , ,

,
=
= 1.93025 x 10
8
= 10
8
molecules (The 10
8
mmHg limits the significant figures.)
5.93 urms =
( ) ( )
( )
3 2 2
3 8.314 J/mol K 273 K
10 g kg m /s
32.00 g/ mol 1 kg J
_ _


, ,
= 461.2878 = 461 m/s
5.94 Molar volume uses exactly one mole of gas along with the temperature and pressure given in the problem.
V / n = RT / P =
( )
( )
L atm
0.0821 730. K
mol K
90 atm
_

, = 0.66592 = 0.67 L/mol
5.95 Determine the total moles of gas produced. The total moles times the fraction of each gas gives the moles of that
gas which may be converted to metric tons.
Moles total = n = PV / RT =
( )
( )
( )
3 3
3 3
1.00 atm 1.5 x 10 m /d
1 L 365.25 d
L atm 1 y 10 m
0.0821 298 K
mol K

_ _


_
, ,

,
= 2.23935 x 10
7
mol/year (unrounded)
Mass CO2 = (0.4896) (2.23935 x 10
7
mol/year) (44.01 g CO2/mol) (1 kg/10
3
g) (1 t/10
3
kg)
= 482.519 = 4.8 x 10
2
t CO2/y
Mass CO = (0.0146) (2.23935 x 10
7
mol/year) (28.01 g CO/mol) (1 kg/10
3
g) (1 t/10
3
kg)
= 9.15773 = 9.16 t CO/y
Mass H2O = (0.3710) (2.23935 x 10
7
mol/year) (18.02 g H2O/mol) (1 kg/10
3
g) (1 t/10
3
kg)
= 149.70995 = 1.50 x 10
2
t H2O/y
Mass SO2 = (0.1185) (2.23935 x 10
7
mol/year) (64.07 g SO2/mol) (1 kg/10
3
g) (1 t/10
3
kg)
= 170.018 = 1.70 x 10
2
t SO2/y
Mass S2 = (0.0003) (2.23935 x 10
7
mol/year) (64.14 g S2/mol) (1 kg/10
3
g) (1 t/10
3
kg)
= 0.4308957 = 4 x 10
1
t S2/y
Mass H2 = (0.0047) (2.23935 x 10
7
mol/year) (2.016 g H2/mol) (1 kg/10
3
g) (1 t/10
3
kg)
= 0.21218 = 2.1 x 10
1
t H2/y
Mass HCl = (0.0008) (2.23935 x 10
7
mol/year) (36.46 g HCl/mol) (1 kg/10
3
g) (1 t/10
3
kg)
= 0.6531736 = 6 x 10
1
t CO2/y
Mass H2S = (0.0003) (2.23935 x 10
7
mol/year) (34.09 g H2S/mol) (1 kg/10
3
g) (1 T/10
3
kg)
= 0.229018 = 2 x 10
1
T CO2/y
20
5.96 The balanced chemical equation is: 2 H2(g) + O2(g) 2 H2O(l)
Moles H2 = (28.0 mol H2O) (2 mol H2/2 mol H2O) = 28.0 mol H2
Moles O2 = (28.0 mol H2O) (1 mol O2/2 mol H2O) = 14.0 mol O2
a) P = nRT / V
P H2 =
( ) ( ) ( )
( )
2
L atm
28.0mol H 0.0821 273.2 23.8 K
mol K
20.0 L
_
+

, = 34.137 = 34.1 atm H2
P O2 =
( ) ( ) ( )
( )
2
L atm
14.0mol O 0.0821 273.2 23.8 K
mol K
20.0 L
_
+

, = 17.06859 = 17.1 atm O2
b) ( )
2
2
n a
P V nb nRT
V
_
+

,
Use Table 5.4 to find the values of the van der Waals constants.
H2: a = 0.244 atmL
2
/mol
2
b = 0.0266 L/mol
O2: a = 1.36 atmL
2
/mol
2
b = 0.0318 L/mol
PVDW =
2
2
nRT n a
V nb V

PVDW H2 =
( ) ( ) ( )
( )
( )
( )
2
2
2
2 2
2
2
atm L
L atm
28.0 mol H 0.244
28.0 mol H 0.08206 273.2 23.8 K
mol
mol K
L
20.0 L
20.0 L 28.0 mol H 0.0266
mol
_
_
+

, ,

,
= 34.9631 = 35.0 atm H2
PVDW O2 =
( ) ( ) ( )
( )
( )
( )
2
2
2
2 2
2
2
atm L
L atm
14.0 mol O 1.36
14.0 mol O 0.08206 273.2 23.8 K
mol
mol K
L
20.0 L
20.0 L 14.0 mol O 0.0318
mol
_
_
+

, ,

,
= 16.78228 = 16.8 atm O2
c) The van der Waals value for hydrogen is slightly higher than the value from the ideal gas equation. The van
der Waals value for oxygen is slightly lower than the value from the ideal gas equation.
5.97 Plan: Deviations from ideal gas behavior are due to attractive forces between particles which reduce the pressure
of the real gas and due to the size of the particle which affects the volume. Compare the size and/or attractive
forces between the substances.
Solution:
a) Xenon would show greater deviation from ideal behavior than argon since xenon is a larger atom than xenon.
The electron cloud of Xe is more easily distorted so intermolecular attractions are greater. Xes larger size also
means that the volume the gas occupies becomes a greater proportion of the containers volume at high pressures.
b) Water vapor would show greater deviation from ideal behavior than neon gas since the attractive forces
between water molecules are greater than the attractive forces between neon atoms. We know the attractive forces
are greater for water molecules because it remains a liquid at a higher temperature than neon (water is a liquid at
room temperature while neon is a gas at room temperature).
c) Mercury vapor would show greater deviation from ideal behavior than radon gas since the attractive forces
between mercury atoms is greater than that between radon atoms. We know that the attractive forces for mercury
are greater because it is a liquid at room temperature while radon is a gas.
d) Water is a liquid at room temperature; methane is a gas at room temperature (think about where you have
heard of methane gas before Bunsen burners in lab, cows digestive system). Therefore, water molecules have
stronger attractive forces than methane molecules and should deviate from ideal behavior to a greater extent than
methane molecules.
21
5.98 Moles of HBr in the Hydrobromic acid: (1.20 mol HBr / L) (3.50 L) = 4.20 mol HBr
V HBr = nRT / P =
( ) ( ) ( )
( )
L atm
4.20 mol HBr 0.0821 273 27 K
mol K
0.975 atm
_
+

, = 106.098 = 106 L HBr
5.99 First, balance the equation:
4 FeS2(s) + 11 O2(g) 8 SO2(g) + 2 Fe2O3(s)
Pressure of N2 = 1.05 atm 0.64 atm O2 = 0.41 atm N2
Pressure of unreacted O2 = (0.64 atm O2) [(100 85)% / 100%] = 0.096 atm O2
Pressure of SO2 produced = (0.64 atm O2) (8 atm SO2 / 11 atm O2) = 0.46545 = 0.47 atm SO2
Total Pressure = (0.41 atm) + (0.096 atm) + (0.46545 atm) = 0.97145 = 0.97 atm total
5.100 Plan: V and T are not given, so the ideal gas equation cannot be used. The total pressure of the mixture is given.
Use PA = XA x Ptotal to find the mole fraction of each gas and then the mass fraction. The total mass of the two
gases is 35.0 g.
Solution:
Ptotal = Pkrypton + Pcarbon dioxide = 0.708 atm
The NaOH absorbed the CO2 leaving the Kr, thus Pkrypton = 0.250 atm
Pcarbon dioxide = Ptotal Pkrypton = 0.708 atm 0.250 atm = 0.458 atm
Determining mole fractions: PA = XA x Ptotal
Carbon dioxide:
CO
2
total
P
X =
P
=
0.458 atm
0.708 atm
= 0.64689 (unrounded)
Krypton:
Kr
total
P
X =
P
=
0.250 atm
0.708 atm
= 0.353107 (unrounded)
Relative mass fraction =
( )
( )
2
83.80 g Kr
0.353107
mol
44.01 g CO
0.64689
mol
1
_
1
,
1
1 _
1
, ]
= 1.039366 (unrounded)
35.0 g = x g CO2 + (1.039366 x) g Kr
35.0 g = 2.039366 x
Grams CO2 = x = (35.0 g) / (2.039366) = 17.16219581 = 17.2 g CO2
Grams Kr = 35.0 g 17.162 g CO2 = 17.83780419 = 17.8 g Kr
5.101 The balanced chemical equations are:
SO2(g) + H2O(l) H2SO3(aq)
H2SO3(aq) + 2 NaOH(aq) Na2SO3(aq) + 2 H2O(l)
Combining these equations gives:
SO2(g) + 2 NaOH(aq) Na2SO3(aq) + H2O(l)
M NaOH = [(mol SO2) (2 mol NaOH / 1 mol SO2) / (L NaOH solution)
Moles SO2 = PV / RT
M NaOH = [(PV / RT) (2 mol NaOH / 1 mol SO2) / (L NaOH solution)
M NaOH =
( ) ( )
( ) ( )
( )
2
2
3
740. mmHg 0.200 L SO
1 atm 2 mol NaOH
L atm 760 mmHg 1 mol SO
0.0821 273 20. K
mol K
10 L
10.0 mL
1 mL

1
1
_ _
1

_ 1
, ,
+

1
, ]
_


,
= 1.619076 = 1.62 M NaOH
22
5.102 a) Moles = n = PV / RT
Moles =
( ) ( )
( ) ( )
30.0 torr 300 L
1 atm
L atm 760 torr
0.0821 273.2 37.0 K
mol K
_

_
,
+

,
= 0.464990 mol (unrounded)
Mass CO2 = (0.464990 mol) (44.01 g/mol) = 20.4642 = 20.5 g CO2
Mass H2O = (0.464990 mol) (18.02 g/mol) = 8.3791 = 8.38 g H2O
b) C6H12O6(s) + 6 O2(g) 6 CO2(g) + 6 H2O(g)
Mass C6H12O6 = (0.464990 mol CO2/h) (1 mol C6H12O6/6 mol CO2) (180.16 g C6H12O6 / 1 mol C6H12O6) (8 h)
= 111.6968 = 1 x 10
2
g C6H12O6 (= body mass lost)
(This assumes the significant figures are limited by the 8 h.)
5.103 a) Derive u
RT
rms

3
M
Set the given relationships equal to each other.
2
1
mu
2
=
3
2
_

, A
R
T
N
Multiply each side by 2 and divide by m.
u
2
=
A
R
T
N
3
m
_

,
u
2
=
3
A
RT
mN
Solve for u by taking the square root of each side; substitute molar mass, M, for mNA (mass of one molecule x
Avogadros number of molecules).
u
RT
rms

3
M
b) Derive Grahams Law
M
M
1
2
2
1

rate
rate

At a given T, the average kinetic energy is equal for two substances, with molecular masses m1 and m2:
k
E
=
2
1

m
1
u
1
2
=
2
1
m
2
u
2
2
m
1
u
1
2
=
m
2
u
2
2
u
2
2
u
1
2
=
m
1
m
2

u
2
u
1
=
m
1
m
2
The average molecular speed, u, is directly proportional to the rate of effusion. Therefore, substitute rate for
each u. In addition, the molecular mass is directly proportional to the molar mass, so substitute M for each m:
M
M
1
2
2
1

rate
rate

5.104 a) cylinder B b) cylinder B c) none d) cylinder C e) cylinder D
23
5.105 Ideal Gas Equation: PV = nRT
P0 = nRT / V =
( ) ( )
( )
3
3
3
1 mol NH L atm
51.1 g NH 0.0821 273 0 K
17.03 g NH mol K
3.000 L
1 _
_
+
1
, 1 , ]
= 22.417687 = 22.4 atm at 0C
P400 = nRT / V =
( ) ( )
( )
3
3
3
1 mol NH L atm
51.1 g NH 0.0821 273 400 K
17.03 g NH mol K
3.000 L
1 _
_
+
1
, 1 , ]
= 55.2641 = 55.3 atm at 400C
van der Waals Equation: ( )
2
2
n a
P V nb nRT
V
_
+

,
NH3: a = 4.17 atmL
2
/ mol
2
b = 0.0371 L/mol
PVDW =
2
2
nRT n a
V nb V

Moles NH3 = (51.1 g NH3) (1 mol NH3 / 17.03 g NH3) = 3.000587 mol NH3 (unrounded)
P0 NH3 =
( ) ( ) ( )
( )
( )
( )
2
2
3
2 3
2
2
atm L
L atm
3.000587 mol NH 4.17
3.000587 mol NH 0.08206 273 0 K
mol
mol K
L
3.000 L
3.000 L 3.000587 mol H 0.0371
mol
_
_
+

, ,

,
= 19.0986 = 19.1 atm NH3
P400 NH3 =
( ) ( ) ( )
( )
( )
( )
2
2
3
2 3
2
2
atm L
L atm
3.000587 mol NH 4.17
3.000587 mol NH 0.08206 273 400 K
mol
mol K
L
3.000 L
3.000 L 3.000587 mol H 0.0371
mol
_
_
+

, ,

,
= 53.2243 = 53.2 atm NH3
5.106 Xmethane = 1.00 Xargon Xhelium = 1.00 0.35 0.25 = 0.40
Pmethane = Xmethane Ptotal = (0.40) (1.75 atm) = 0.70 atm CH4
Moles x Avogadros number = molecules
Moles = PV / RT
Molecules =
( ) ( )
( ) ( )
23
4
0.70 atm 6.0 L 6.022 x 10 molecules CH
L atm 1 mol
0.0821 273 45 K
mol K
_


_
,
+

,
= 9.6876795 x 10
22
= 9.7 x 10
22
molecules CH4
5.107 Plan: Find the number of moles of carbon dioxide produced by converting the mass of glucose in grams to moles
and using the stoichiometric ratio from the balanced equation. Then use the T and P given to calculate volume
from the ideal gas equation.
Solution:
a) C6H12O6(s) + 6 O2(g) 6 CO2(g) + 6 H2O(g)
Moles CO2: ( )
6 12 6 2
6 12 6
6 12 6 6 12 6
1 mol C H O 6 mol CO
18.0 g C H O
180.16 g C H O 1 mol C H O
_ _

, ,
= 0.599467 mol CO2
24
V =
nRT
P
=
( ) ( ) ( )
( )
L atm
0.599467 mol 0.0821 273 35 K
760 torr mol K
780. torr 1 atm
_
+

_
,

,
= 14.76992 = 14.8 Liters CO2
This solution assumes that partial pressure of O2 does not interfere with the reaction conditions.
b) Plan: From the stoichiometric ratios in the balanced equation, calculate the moles of each gas and then use
Daltons law of partial pressures to determine the pressure of each gas.
Solution:
Moles CO2 = Moles O2 = ( )
6 12 6
6 12 6
6 12 6 6 12 6
1 mol C H O 6 mol
9.0 g C H O
180.16 g C H O 1 mol C H O
_ _

, ,
= 0.299734 mol CO2 = mol O2
At 35C, the vapor pressure of water is 42.2 torr. No matter how much water is produced, the partial pressure of
H2O will still be 42.2 torr. The remaining pressure, 780 torr 42.2 torr = 737.8 torr (unrounded) is the sum of
partial pressures for O2 and CO2. Since the mole fractions of O2 and CO2 are equal, their pressures must be equal,
and be onehalf of sum of the partial pressures just found.
Pwater = 42.2 torr
(737.8 torr) / 2 = 368.9 = 3.7 x 10
2
torr Poxygen = Pcarbon dioxide
5.108 a) Assuming the total pressure is 760 torr.
(0.2 torr Br2 / 760 torr) (10
6
) = 263.15789 = 300 ppm Br2 Unsafe
b) Assuming the total pressure is 760 torr.
(0.2 torr CO2 / 760 torr) (10
6
) = 263.15789 = 300 ppm CO2 Safe
c) Moles bromine = (0.0004 g Br2) (1 mol Br2 / 159.80 g Br2) = 2.5031 x 10
6
mol Br2 (unrounded)
Moles air = PV / RT =
( ) ( )
( )
1.00 atm 1000 L
L atm
0.0821 273 K
mol K
_

,
= 44.616 mol air (unrounded)
Concentration of Br2 = [(2.5031 x 10
6
mol) / (44.616 mol)] (10
6
) = 0.056103 = 0.06 ppm Br2 Safe
d) Moles CO2 = (2.8 x 10
22
molecules CO2) (1 mol CO2 / 6.022 x 10
23
molecules CO2)
= 0.046496 mol CO2 (unrounded)
Concentration of CO2 = [(0.046496 mol) / (44.616 mol)] (10
6
) = 1042.1 = 1.0 x 10
3
ppm CO2 Safe
5.109 4 NH3(g) + 4 NO(g) + O2(g) 4 N2(g) + 6 H2O(g)
a)
( )
( )
( ) ( )
5
3
4.5 x 10 atm 1.00 L
4 L NH
L atm 4 L NO
0.0821 273 150 K
mol K

_

_
,
+

,
= 1.29577 x 10
6
= 1.3 x 10
6
L NH3 for every liter of polluted air
b)
( )
( )
( ) ( )
5
3
3 3
3
4.5 x 10 atm 1 kL
4 mol NH 17.03 g NH 10 L
L atm 1 kL 4 mol NO 1 mol NH
0.0821 273 150 K
mol K

_ _ _


_
, , ,
+

,
= 0.022067 = 0.022 g NH3
5.110
Rate Ne
Rate Xe
=
Molar Mass Xe
Molar Mass Ne
=
131.3 g/mol
20.18 g/mol
= 2.55077 enrichment factor (unrounded)
Thus XNe = (2.55077) / (2.55077 + 1) = 0.7183709 = 0.7184
25
5.111 Plan: To find the number of steps through the membrane, calculate the molar masses to find the ratio of
effusion rates. This ratio is the enrichment factor for each step.
Solution:
235
UF
6
238
UF
6
Rate
Rate
=
238
6
235
6
Molar Mass UF
Molar Mass UF
=
352.04 g/ mol
349.03 g/mol
= 1.004302694 enrichment factor (unrounded)
Therefore, the abundance of
235
UF6 after one membrane is 0.72% x 1.004302694;
Abundance of
235
UF6 after N membranes = 0.72% * (1.004302694)
N
Desired abundance of
235
UF6 = 3.0% = 0.72% * (1.004302694)
N
Solving for N:
4.16667 = (1.004302694)
N
ln 4.16667 = ln (1.004302694)
N
ln 4.16667 = N * ln (1.004302694)
N = (ln 4.16667) / (ln 1.004302694) = 332.392957 = 332 steps
5.112 Plan: The amount of each gas that leaks from the balloon is proportional to its effusion rate. Using 45% as the
rate for H2, the rate for O2 can be determined from Grahams Law.
Solution:
2
2
Rate O
Rate H
=
2
2
Molar Mass H
Molar Mass O
=
2.016 g/ mol
32.00 g/mol
=
2
Rate O
45
Rate O2 = 0.250998(45) = 11.2949 (unrounded)
Amount of H2 that leaks = 45%; 10045 = 55% H2 remains
Amount of O2 that leaks = 11.2949%; 10011.2949 = 88.705% O2 remains
2
2
O 88.705
=
H 55
= 1.6128 = 1.6
5.113 a) Options for PCl3:
All values are g/mol
P First Cl Second Cl Third Cl Total
31 35 35 35 136
31 37 35 35 138
31 37 37 35 140
31 37 37 37 142
b) Rate P
37
Cl3 / Rate P
35
Cl3 =
3
37
3
35
Cl P Mass Molar
Cl P Mass Molar
=
136 g/ mol
142 g/ mol
= 0.978645 = 0.979
5.114 a) Pf = PiTf / Ti = (35.0 psi) (319 K) / (295 K) = 37.847 = 37.8 psi
b) New tire volume = Vi (102% /100%) = 1.02 Vi = Vf
Pf = PiViTf / TiVf = [(35.0 psi) (Vi) (319 K)] / [(295 K) (1.02 Vi)] = 37.105 = 37.1 psi
c) n = PV / RT =
( ) ( ) ( )
( )
37.105 35.0 psi 208 L
1 atm
L atm 14.7 psi
0.0821 295 K
mol K

_

_
,

,
= 1.229795579 mol lost (unrounded)
Time = (1.229795579 mol) (28.8 g/mol) (1 min / 1.5 g) = 23.612 = 24 min
5.115 a) n = PV / RT =
( ) ( )
( )
85.0 atm 850. L
80.0%
L atm 100%
0.0821 298 K
mol K
_

_ ,

,
= 2.36248 x 10
3
= 2.36 x 10
3
mol Cl2
26
b) ( )
2
2
n a
P V nb nRT
V
_
+

,
PVDW =
2
2
nRT n a
V nb V

Use Table 5.4 to find the values of the van der Waals constants.
Cl2: a = 6.49 atmL
2
/mol
2
b = 0.0562 L/mol
( )
( )
( )
( )
( )
2
2
3
3
2
2 2
2
3
2
atm L
L atm
2.36248 x 10 mol Cl 6.49
2.36248 x 10 mol Cl 0.08206 298 K
mol
mol K
L
850. L
850. L 2.36248 x 10 mol Cl 0.0562
mol
_
_


, ,

,
= 30.4134 = 30.4 atm
c) The engineer did not completely fill the tank. She should have filled it to (80.0%/100%) (85.0 atm) = 68 atm,
but only filled it to 30.4 atm.
27